JP7344074B2 - Impact-resistant polyamide molding compound - Google Patents

Description

In addition to certain amorphous polyamides and functionalized styrene-butadiene-styrene-triblock copolymers as impact modifiers, the present invention optionally further comprises certain partially crystalline polyamides and additives. The present invention relates to an impact-modified polyamide molding material comprising: The invention also relates to the use of these polyamide molding materials for producing molded articles.

Polyamides are commonly used today as components for interiors and exteriors, in particular in the field of housings, optics and displays, but also in the field of household appliances and sports equipment. This is essentially due to the good mechanical properties of polyamide. This is important for good processability of the molding material in order to allow a wide variety of shapes. At the same time, however, it is also important to enable good optical properties of the molding composition (particularly regarding transparency), which should be maintained even after a fairly long period of use.

EP 3 336 131 A1 discloses polyamide molding compositions based on amorphous polyamides which have good processability and likewise good optical properties. This amorphous polyamide can also be modified with an aliphatic polyamide.

EP 2 778 190 B1 contains a polyamide selected from the group consisting of PA MACM12, PA PACM12, PA MACM10, PA PACM10, PA MACM14 and PA PACM14, mixtures thereof and copolyamides, and as an impact modifier, A transparent blend of functionalized styrene-ethylene/butylene-styrene block copolymer (SEBS) is disclosed, which exhibits high notch impact strength.

EP 3 336 131 A1 EP 2 778 190 B

Starting from this, the object of the invention is, in addition to high stiffness (expressed in particular by the tensile modulus), high strength (expressed in particular by notch impact strength) and very good optical properties (in particular , haze and light transmittance).

This object is achieved by a polyamide molding composition having the features of claim 1. Further dependent claims reveal advantageous developments.

According to the present invention, there is provided a polyamide molding material comprising or consisting of the following components (A) to (D):
(A) 55 to 97% by weight of at least one amorphous copolyamide formed from monomers (a1) to (a4):
(a1) 25 to 40 mol% of at least one acyclic aliphatic diamine having 6 to 10 carbon atoms;
(a2) 10 to 25 mol% of at least one alicyclic diamine having 6 to 36 carbon atoms;
(a3) 20 to 40 mol% of at least one aromatic dicarboxylic acid;
(a4) 10 to 30 mol% of at least one acyclic aliphatic dicarboxylic acid having 8 to 16 carbon atoms;
Here, the ratio of the monomers (a1) and (a2) is related to the total diamine used, and the total is 50 mol%, and the ratio of the monomers (a3) and (a4) is the dicarboxylic acid used. The total amount is 50 mol%;
(B) 3-22% by weight of at least one functional styrene-butadiene-styrene-triblock copolymer;
(C) 0 to 15% by weight of at least one aliphatic partially crystalline polyamide selected from the group consisting of PA6/12 and PA612; and (D) 0 to 8% by weight of at least one addition. Agent Here, the proportions of the components (A) to (D) are 100% by weight in total.

Definition of Terms - Notations and Abbreviations for Polyamides and Their Monomers In the sense of the present invention, the term "polyamide" (abbreviation PA) is understood as a general term and includes homopolyamides and copolyamides. The designations and abbreviations chosen for polyamides and their monomers correspond to those defined in ISO Standard 16396-1 (2015, (D)). The abbreviations used therein are used synonymously below with the IUPAC names of the monomers.

- Description of general amounts The polyamide molding material according to the present invention contains or consists of components (A) and (B), and optionally (C)/(D), B), (C) and (D) must total 100% by weight. The specified ranges for the amounts of individual components (A), (B), (C) and (D) are as follows: It is understood that any amount of each component can be selected within the predetermined ranges.

・Functionalization (functionalization) of component (B)
Component (B) can be functionalized by copolymerization or by grafting. In the sense of the present invention, functionalization by copolymerization means the incorporation of a functionalized compound into the main chain of component (B) as a component of this main chain. Functionalization of component (B) by grafting, on the other hand, is understood as attaching a functionalized compound to the main chain in such a way that a side chain is formed.

- Partially crystalline polyamide In the sense of the present invention, a partially crystalline polyamide is a polyamide that has a melting point.
In the sense of the present invention, partially crystalline polyamides are characterized in dynamic differential calorimetry (differential scanning calorimetry; DCS) according to ISO 11357-3 (2013) at a heating rate of 20 K/min, preferably from 4 J/g. It is a polyamide that exhibits a large heat of fusion.

Polyamide molding material The polyamide molding material according to the invention comprises or consists of components (A) and (B), and optionally component (C) and/or component (D).

According to a preferred embodiment of the invention, the proportion of component (A) in the polyamide molding material is from 61 to 97% by weight, preferably from 67 to 93% by weight, particularly preferably from 67 to 93% by weight, based on the total weight of the polyamide molding material. It is in the range of 77 to 90.9% by weight.

According to a further preferred embodiment of the invention, the proportion of component (B) in the polyamide molding material is from 3 to 20% by weight, preferably from 4 to 17% by weight, particularly preferably from 4 to 17% by weight, based on the total weight of the polyamide molding material. is in the range of 4 to 10% by weight.

According to a further preferred embodiment, the proportion of component (C) in the polyamide molding material is from 0 to 13% by weight, preferably from 3 to 12% by weight, particularly preferably from 5 to 12% by weight, based on the total weight of the polyamide molding material. It is in the range of 10% by weight.

According to a further preferred embodiment, the proportion of component (D) in the polyamide molding material is from 0 to 6% by weight, preferably from 0 to 4% by weight, particularly preferably from 0.5% by weight, based on the total weight of the polyamide molding material. It is in the range of 1 to 3% by weight.

The haze of the polyamide molding material, measured according to ASTM D1003 on a molded article (width and length: 60 x 60 mm 2 mm thick plate) manufactured from the polyamide molding material, is at most 20%, preferably at most 15%. , particularly preferably at most 10%.

A molded article (width and length: 60 x 60 mm 2 mm thick plate) produced from the polyamide molding compound has a light transmission measured according to ASTM D1003 of at least 80%, preferably at least 85%, particularly preferably at least It will be 90%.

The molded articles produced from the polyamide molding compositions preferably have a tensile modulus measured according to ISO 527 of at least 1500 MPa, preferably at least 1700 MPa, particularly preferably at least 1800 MPa.

The molded articles produced from the polyamide molding composition preferably have a notch impact strength measured according to DIN EN ISO 179/2eA of at least 18 kJ/m ² , preferably 21 kJ/m ² .

According to a preferred embodiment of the invention, the polyamide molding composition according to the invention does not contain glass fibers.

In a particularly preferred embodiment, the polyamide molding composition according to the invention does not contain fibrous fillers.

According to a preferred embodiment, component (A) consists of only one copolyamide and component (B) consists of only one impact modifier.

According to a preferred embodiment, component (A) consists of only one copolyamide, component (B) consists of only one impact modifier, and component (C) consists of one aliphatic partially crystalline polyamide. Consists only of

Ingredient (A)
Component (A) consists of at least one amorphous copolyamide formed from monomers (a1) to (a4):
(a1) 25 to 40 mol% of at least one acyclic aliphatic diamine having 6 to 10 carbon atoms;
(a2) 10 to 25 mol% of at least one alicyclic diamine having 6 to 36 carbon atoms;
(a3) 20 to 40 mol% of at least one aromatic dicarboxylic acid;
(a4) 10 to 30 mol% of at least one acyclic aliphatic dicarboxylic acid having 8 to 16 carbon atoms;
Here, the ratio of the monomers (a1) and (a2) is related to the total diamine used, and the total is 50 mol%, and the ratio of the monomers (a3) and (a4) is the dicarboxylic acid used. The total amount is 50 mol%.

According to a preferred embodiment of the invention, monomer (a1) is a linear or branched diamine having 6 to 8 carbon atoms, particularly preferably 1,6-hexamethylenediamine and/or 2-methyl- 1,5-pentanediamine.

The monomer (a2) is preferably an alicyclic diamine having 12 to 20 carbon atoms, preferably bis(4-amino-3-methylcyclohexyl)methane (MACM), bis(4-aminocyclohexyl) Methane (PACM), 2,2-bis(4-aminocyclohexyl)propane (PACP), 2,2-bis(4-amino-3-methylcyclohexyl)propane (MACP), bis(4-amino-3-ethyl) cyclohexyl)methane (EACM), 2,2-bis-(4-amino-3-ethyl-cyclohexyl)propane (EACP), bis(4-amino-3,5-dimethylcyclohexyl)methane (TMACM), 2,2 -bis(4-amino-3,5-dimethylcyclohexyl)propane (TMACP) and mixtures thereof, wherein bis(4-amino-3-methylcyclohexyl)methane (MACM), bis( Particular preference is given to 4-aminocyclohexyl)methane (PACM) and mixtures thereof.

The monomer (a3) is preferably an aromatic dicarboxylic acid having 6 to 36 carbon atoms, preferably terephthalic acid (TPS), naphthalene dicarboxylic acid (NDA) (including 1,5-naphthalene dicarboxylic acid). and 2,6-naphthalenedicarboxylic acid), isophthalic acid (IPS), biphenyldicarboxylic acid, particularly preferably diphenyl-2,2'-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 3,3 '-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, and 4,4'-diphenylsulfonedicarboxylic acid, 1,5-anthracenedicarboxylic acid, p-terphenylene-4, It is selected from the group consisting of 4''-dicarboxylic acids and 2,5-pyridinedicarboxylic acids and mixtures thereof, with terephthalic acid and isophthalic acid and mixtures thereof being highly preferred.

The monomer (a4) is preferably an acyclic linear or branched aliphatic dicarboxylic acid having 10 to 14 carbon atoms, preferably decanedioic acid, undecanedioic acid, dodecanedioic acid, It is selected from the group consisting of tridecanedioic acid, tetradecanedioic acid and mixtures thereof, in particular it is particularly preferred to use dodecanedioic acid, very preferably only dodecanedioic acid is used.

As monomer (a3) a mixture of terephthalic acid and isophthalic acid can preferably be used, preferably in a molar ratio of 2:1 to 1:2, in particular in a ratio of 1.5:1 to 1:1.5, very An equimolar mixture of terephthalic acid and isophthalic acid is preferably used.

The proportion of monomer (a1) in the copolyamide is preferably in the range 27.5 to 40 mol%, preferably in the range 30 to 38.5 mol%, and/or of monomer (a2) in the copolyamide. The proportion is preferably in the range from 10 to 22.5 mol%, particularly preferably in the range from 11.5 to 20 mol%, in which case the proportion of monomers (a1) and (a2) is based on the total amount of diamines used. The total amount is 50 mol%.

The proportion of monomer (a3) in the copolyamide is preferably in the range from 25 to 40 mol%, preferably in the range from 30 to 37.5 mol%, and/or the proportion of monomer (a4) in the copolyamide is , preferably in the range from 10 to 25 mol %, particularly preferably in the range from 12.5 to 20 mol %, the proportion of monomers (a3) and (a4) being with respect to the total dicarboxylic acids used. The total amount is 50 mol%.

According to a further preferred embodiment,
- said monomer (a1) is selected as 1,6-hexamethylene diamine;
- said monomer (a2) is selected from the group consisting of bis(4-amino-3-methylcyclohexyl)methane (MACM), bis(4-amino-cyclohexyl)methane (PACM) and mixtures thereof, preferably; Only bis(4-amino-3-methylcyclohexyl)methane (MACM) is selected;
- said monomer (a3) is selected from the group consisting of terephthalic acid, isophthalic acid and mixtures thereof, preferably a mixture in a ratio of 1.5:1 to 1:1.5, particularly preferably an equimolar mixture is;
- Said monomer (a4) is selected as dodecanedioic acid.

Preferably, the proportions of said monomers are selected as follows:
・(a1) Range of 30 to 37.5 mol% ・(a2) Range of 12.5 to 20 mol% ・(a3) Range of 30 to 37.5 mol% ・(a4) 12.5 to 20 mol% Here, the proportion of monomers (a1) and (a2) is related to the total diamine used, which is 50 mol% in total, and the proportion of monomer (a3) and (a4) is related to the total diamine used. The total amount is 50 mol%.

In general, it is preferred that within the scope of component (A) no lactam-based or amino acid-based components are used. Component (A) is therefore essentially free of lactam and/or amino acid components (ie a proportion of less than 2% by weight, preferably less than 1% by weight, relative to the total amount of (A)). Preferably, component (A) does not contain any lactam and/or amino acid components.

Particularly preferred copolyamides (A) are composed of the following monomers:
- (a1) 1,6-hexamethylene diamine in the range of 30 to 33 mol%;
- (a2) MACM in the range of 17 to 20 mol%;
- (a3) an equimolar mixture of terephthalic acid and isophthalic acid in the range of 29.5 to 32.5 mol%;
- (a4) dodecanedioic acid in the range of 17.5 to 20.5 mol%;
Here, the ratio of monomers (a1) and (a2) is related to the total of diamines used, which is 50 mol% in total, and the ratio of monomers (a3) and (a4) is the total of dicarboxylic acids used. The total amount is 50 mol%.

Furthermore, component (A) has a relative viscosity of 1.50 to 1.90, particularly preferably 1.60 to 1.80 and very preferably 1.65 to 1.80 (according to ISO 307 (2013) 20 0.5 g of polymer in 100 mL of m-cresol) and/or component (A) has a relative viscosity of at least 100° C., preferably at 120° C. It is preferable to have a glass transition point of 130° C. or higher, particularly preferably 140° C. or higher (but preferably 220° C. or lower, or 200° C. or lower), where the glass transition point is according to ISO 11357-2 (2013): Measured by DSC at a heating rate of 20 K/min.

The copolyamide according to component (A) is amorphous and has an unmeasurable or very low heat of fusion (enthalpy of fusion), preferably below 4 J/g, particularly preferably below 2 J/g, very preferably 1 J/g) (measured by differential scanning calorimetry (DSC) at a heating rate of 20 K/min of the granules according to ISO 11357-3 (2013)).

Ingredient (B)
According to a preferred embodiment of the invention, the functionalization of component (B) is carried out by copolymerization and/or by grafting. For this purpose, particular preference is given to using compounds selected from the group consisting of unsaturated carboxylic acids, unsaturated carboxylic acid derivatives and mixtures thereof and/or unsaturated glycidyl compounds. These are particularly preferably unsaturated carboxylic esters, in particular acrylic esters and/or methacrylic esters, unsaturated carboxylic acid anhydrides, especially maleic anhydride, glycidyl acrylic acid, glycidyl methacrylic acid, α-ethyl acrylic acid. , maleic acid, fumaric acid, itaconic acid, citraconic acid, aconitic acid, tetrahydrophthalic acid, butenylsuccinic acid, and mixtures thereof.

If the functionalization is carried out by copolymerization, the weight proportion of the individual compounds used for the functionalization is preferably from 3 to 20% by weight, in each case based on the total weight of component (B), particularly preferably It ranges from 5 to 16% by weight, and more preferably from 6 to 14% by weight.

If the functionalization is carried out by grafting, the weight proportion of the individual compounds used for the functionalization is preferably from 0.4 to 2.0% by weight in each case, based on the total weight of component (B). The range is particularly preferably from 0.6 to 1.6% by weight, and even more preferably from 0.8 to 1.4% by weight.

Impact modifiers functionalized by copolymerization can also be further functionalized by grafting.

Styrene-butadiene-styrene-triblock copolymer is a linear triblock copolymer consisting of one butadiene block and two styrene blocks.

The proportion of styrene in the styrene-butadiene-styrene triblock copolymer is preferably from 25 to 53% by weight, particularly preferably from 30 to 48% by weight and very preferably from 35 to 45% by weight.

The styrene-butadiene-styrene-triblock copolymer preferably has a melt flow rate (MFR) of 4 to 25 g/10 min, particularly preferably 5 to 20 g/10 min, very preferably 6 to 15 g/10 min. have The melt flow rate is measured at 200° C. and 5 kg according to ISO1133.

The proportion of styrene in the styrene-butadiene-styrene triblock copolymer is preferably 25 to 53% by weight, particularly preferably 30 to 48% by weight, very preferably 35 to 45% by weight, and/or The styrene-butadiene-styrene-triblock copolymer contains 0.4 to 2.0% by weight, particularly preferably 0.6 to 1.6% by weight, even more preferably 0.8 to 1.4% by weight of maleic anhydride. and/or said styrene-butadiene-styrene-triblock copolymer is preferably 4 to 25 g/10 min, particularly preferably 5 to 20 g/10 min, very preferably 6 to 15 g/10 min. It has a melt flow rate (MFR) of 10 minutes.

The styrene-butadiene-styrene-triblock copolymer is preferably produced by anionic polymerization using butyllithium as an initiator. This results in 36-38% cis-1,4-units, 52-53% trans-1,4-units, and 10-12% 1,2-units within the butadiene block.

The styrene-butadiene-styrene triblock copolymers may also be used in hydrogenated, crosslinked or vulcanized form in the polyamide molding compositions according to the invention.

The at least one styrene-butadiene-styrene-triblock copolymer according to component (B) is in the form of a mixture or blend, i.e. with one or more non-functionalized styrene-butadiene-styrene-triblock copolymers; It may also be used in the form of a homogenized mixture in melt, the weight proportions of the functionalization still being within the ranges mentioned above for functionalization by copolymerization or by grafting.

However, according to a preferred embodiment, the polyamide molding composition according to the invention does not contain non-functionalized styrene-butadiene-styrene triblock copolymers.

Ingredient (C)
According to a preferred embodiment, component (C) has a relative viscosity of 1.50 to 2.25, preferably 1.65 to 2.10, particularly preferably 1.75 to 2.00. The relative viscosity is determined according to ISO 307 (2007) at 20° C. in a solution of 0.5 g of polymer in 100 ml of m-cresol.

According to a further preferred embodiment, component (C) has a melting point of 120-225°C, preferably 180-210°C, particularly preferably 190-200°C, wherein said melting point is in accordance with ISO 11357-3 (2013) by DSC at a heating rate of 20 K/min.

In another preferred embodiment, component (C) is the copolyamide PA6/12, formed from ε-caprolactam and 12-laurinlactam.

The PA6/12 preferably comprises 96 to 75 mol% ε-caprolactam and 4 to 25 mol% laurinlactam, particularly preferably 94 to 80 mol% ε-caprolactam and 6 to 20 mol% laurinlactam. very preferably from 92 to 82 mol % of ε-caprolactam and from 8 to 18 mol % of laurinlactam.

In a particularly preferred embodiment, component (C) has a melting point of 200° C., a relative viscosity of 1.80 to 2.00, and is formed from 90 mol% ε-caprolactam and 10 mol% 12-laurinlactam. copolyamide 6/12, where the melting point is determined by DCS according to ISO 11357-3 (2013) at a heating rate of 20 K/min and the relative viscosity is determined at 20 °C according to ISO 307 (2007). , measured in a solution containing 0.5 g of polymer in 100 mL of m-cresol.

Ingredient (D)
According to a preferred embodiment of the invention, additives (D) are inorganic and organic stabilizers, in particular antioxidants, antiozonants, photoprotectants, in particular UV stabilizers, UV absorbers or UV blockers. , lubricants, colorants, marking agents, pigments, carbon black, graphite, graphene, carbon nanotubes, photochromic agents, antistatic agents, mold release agents, condensation catalysts, chain regulators, antifoaming agents, antiblocking agents, chain extenders Additives, optical brighteners, IR absorbers, NIR absorbers, halogen-containing flame retardants, non-halogen flame retardants, natural layered silicates, synthetic layered silicates, metallic pigments, metal flakes, metal-coated particles, granular fillers , fibrous fillers, nanoscale fillers (having a particle size (d ₉₅ ) of 100 nm or less as determined by laser diffraction according to ISO 13320 (2009)), and mixtures thereof.

The layered silicates and fillers may be surface treated. This can be done using a suitable sizing system or adhesive system. For this purpose, systems based on fatty acids, waxes, silanes, titanates, polyamides, urethanes, polyhydroxy ethers, epoxides, nickel, combinations of each or mixtures thereof can be used, for example.

As particulate fillers all fillers known to the person skilled in the art can be used. For this, in particular, the minerals talc, mica, dolomite, silicates, quartz, titanium dioxide, wollastonite, kaolin, silicic acid, magnesium carbonate, magnesium hydroxide, chalk, powdered glass, glass flakes, powdered carbon fiber , heavy or precipitated calcium carbonate, lime, feldspar, barium sulphate, zinc sulphide, zinc oxide, permanent magnets or magnetizable metals or alloys, glass spheres, hollow glass spheres, hollow spherical silicate fillers and mixtures thereof. and particulate fillers selected from the group.

According to a particularly preferred embodiment of the invention, additives (D) are inorganic and organic stabilizers, in particular antioxidants, antiozonants, photoprotectants, in particular UV stabilizers, UV absorbers or UV Blocking agents, lubricants, colorants, marking agents, pigments, photochromic agents, antistatic agents, mold release agents, condensation catalysts, chain regulators, antifoaming agents, antiblocking agents, chain extension additives, optical brighteners, IR absorbers, NIR absorbers, natural layered silicates, synthetic layered silicates, granular fillers, nanoscale fillers (with a particle size (d ₉₅ ) of less than 100 nm as determined by laser diffraction according to ISO 13320 (2009)) ) and mixtures thereof.

Said additive (D) preferably comprises from 0.1 to 6% by weight, and particularly preferably from 0.2 to 4% by weight, based on the total weight of the polyamide molding material.

Molded Article The molded article according to the invention can be produced from the polyamide molding composition according to the invention by current processing techniques, such as injection molding.

According to a preferred embodiment of the invention, the molded article is a decorative article, in particular a decorative article in the interior of a car and in the fashion field, a sports article, in particular ski boots, soles of sports shoes, leisure articles, toys, in particular structural elements. , components, figures or models, household items, especially containers, dishes, bowls, cans, beakers, baby bottles, drinking bottles, components of kitchen utensils, components of eyeglasses, especially eyeglass frames or side pieces of eyeglasses (especially (for safety goggles, sports goggles or ski goggles), furniture covers, insoles, components and fittings for instruments in the hygiene and cosmetics sector, parts for safety shoes, in particular caps, filter cups, examination glasses, flow meters. , bursting discs, containers, housings or housing parts for electrical and electronic equipment, in particular shaving instruments, hair removal instruments, measuring instruments, infrared keys, mobile phones, players, personal digital assistants (PDAs), smartphones or storage media (e.g. USB housings or housing parts for sticks), protective covers for mobile phones, trim parts in the computer and telecommunications sector, pipes, hoses, and parts for electronic cigarettes.

Further, the present invention provides the use of the above-mentioned polyamide molding material according to the present invention in decorative articles, especially decorative articles in the interior of automobiles and in the fashion field, sports articles, especially ski boots, soles of sports shoes, leisure articles, toys, in particular structural elements, components, figures or models, household items, in particular containers, dishes, bowls, cans, beakers, baby bottles, drinking bottles, components of kitchen utensils, components of eyeglasses, in particular eyeglass frames or eyeglass sides pieces (in particular for safety goggles, sports goggles or ski goggles), furniture covers, insoles, components and fittings for instruments in the hygiene and cosmetics sector, parts for safety shoes, in particular caps, filter cups, examination glasses , flowmeters, rupture discs, containers, housings or housing parts for electrical and electronic equipment, in particular shaving instruments, hair removal instruments, measuring instruments, infrared keys, mobile phones, players, personal digital assistants (PDAs), smartphones or storage media ( For example, it relates to the use for manufacturing housings or housing parts for USB sticks), protective covers for mobile phones, trim parts in the computer and telecommunications sector, pipes, hoses, and parts for electronic cigarettes.

The subject matter of the invention will be explained in more detail with reference to the examples given below, but the subject matter is not limited to the particular embodiments shown here.

Measurement method /relative viscosity Relative viscosity was measured at 20°C according to ISO307 (2007). For this purpose, 0.5 g of polymer granules were weighed into 100 mL of m-cresol. Calculation of relative viscosity (RV) was performed according to chapter 11 of the standard, RV=t/t ₀ .

・Melting point and glass transition point (Tg)
Melting point measurements were performed on granules according to ISO 11357-3 (2013).
Differential scanning calorimetry (DSC) was performed at a heating rate of 20 K/min in each of the two heating runs. After the initial heating, the samples were quenched with dry ice. The melting point was measured during the second heating.
The temperature of the peak maximum value was shown as the melting point. The center of the glass transition range is designated as the glass transition temperature (Tg), which was measured by the "half height" method.

・Tensile modulus The tensile modulus was measured using an ISO tensile test piece (type A1, size 170 ×20/10×4).

・Charpy notch impact strength The measurement of the notch impact strength by Charpy was performed using ISO test specimens, type B1 (dimensions 80 x 10 x 4 mm).

・Light transmittance and haze Light transmittance and haze were measured at 23°C, according to ASTM D 1003 (2013), with a 2 mm thick 60 mm x 60 mm plate (width x length), and by Byk Gardner's "Haze Gard plus". ” (using CIE illuminant C). The value of light transmittance was expressed as % of the amount of irradiated light.

・MVR (melt volume rate) or MFR (melt flow rate)
MVR or MFR measurements were carried out on impact modifier granules according to ISO 1133-1 (2012) using the temperatures and loads shown in Table 1.

- Manufacture of test pieces Test pieces were manufactured using granules with a water content of less than 0.1% by weight. The test specimens were produced on an Arburg injection molding machine Allrounder 420 C 1000-250. In this case, a rising or falling cylinder temperature was used from the feed port to the nozzle.

ISO tensile test piece and ISO test piece Cylinder temperature: 260/265/270/275/280/275℃
Mold temperature: 80℃
60x60x2mm plate
Cylinder temperature: 270/275/280/285/290/285℃
Mold temperature: 80℃

A polished mold was used to manufacture the plate.
The specimens were used in a dry state unless stated otherwise; for this, the specimens were incubated in a dry environment (i.e. on silica gel) at room temperature for at least 48 hours after injection molding. I kept it.

Starting Materials The materials used in the Examples and Comparative Examples are summarized in Tables 1 and 2.

Examples and comparative examples
General production details of copolyamide (A)
The production of the transparent copolyamides according to the invention is carried out in a known manner in a pressurized autoclave with a known stirrable receiving vessel and a reaction vessel.

Into the receiving tank, place deionized water and add monomer and optional additives. The atmosphere is then made inert multiple times using nitrogen gas. Heat under controlled pressure at 180-230° C. with stirring to obtain a homogeneous solution. This solution is pumped through a sieve into the reaction vessel and heated at the desired reaction temperature of 270-310° C. and a pressure of up to 30 bar. The batch is held in the pressure phase at the reaction temperature for 2 to 4 hours. In a subsequent pressure release phase, within 1-2 hours, the pressure is reduced to atmospheric pressure, with the temperature possibly dropping slightly. In the subsequent degassing phase, the batch is kept at a temperature of 250-310° C. for 0.5-3 hours at atmospheric pressure. The polymer melt is discharged in the form of strands, cooled to 10-80° C. in a water bath and granulated. Dry the granules at 60-120° C. under nitrogen or in vacuum to a moisture content of less than 0.1% by weight.

General production details for polyamide molding materials To produce the polyamide molding materials according to the invention, components (A), (B) and optionally (C) and/or (D) are mixed in a conventional compounding machine ( For example, a single screw or twin screw extruder or a screw kneader is used for mixing. The components are then metered individually into the feed ports via gravimetric or volumetric scales, or respectively metered into side feeders, or are fed in the form of a dry blend.

If additives (component (D)) are used, these can be introduced directly or in the form of a masterbatch. The carrier material of the masterbatch is preferably a polyamide or polyolefin. Among the polyamides mentioned, the polyamides of component (A) are particularly suitable for this purpose.

To produce the dry blend, the dry granules of components (A), (B), and optionally (C) and/or (D) are mixed in one closed container. The mixture is homogenized for 10 to 40 minutes with a tumble mixer, drum hoop mixer or tumble dryer. This may be done under dry protective gas to avoid absorption of moisture.

The compounding is carried out at a set cylinder temperature of 250-310°C, where the temperature of the first cylinder may be adjusted below 90°C. Degassing can be done in front of the nozzle. This can be done by vacuum or atmospheric action. The melt is discharged in the form of strands, cooled to 10-80° C. in a water bath and then granulated. The granules are dried under nitrogen or in vacuum at 60-120° C. until the moisture content is less than 0.1% by weight.

Preparation of Polyamide Molding Material of Example 1 Dry granules of components (A) and (B) and additive (D) were mixed in the ratios shown in Table 3 to form a dry blend. This mixture was homogenized with a tumble mixer for approximately 20 minutes.

The polyamide molding composition was produced in a twin-screw extruder type ZSK 25 from Werner & Pfleiderer. The dry blend was metered into the feed port via a weighing scale.

The temperature of the first housing was adjusted to 50°C, and the temperature of the remaining housings was adjusted to 270-290°C. A rotation speed of 200 rpm and a throughput of 10 kg/h were used. No degassing was performed. The molten strand was cooled in a water bath and cut, and the resulting granules were dried at 80° C. in vacuum (30 mbar) for 24 hours to a water content of less than 0.1% by weight.

Test Results All Examples and Comparative Examples contain 0.3% by weight of additives, which are each composed of 0.1% by weight of stabilizers 1 to 3.
The molding material according to the invention was tested under the measurement conditions described above for tensile modulus, notch impact strength, haze and light transmittance.

The results of these tests are shown in Table 3.

Similarly, molding materials not according to the invention were tested with respect to tensile modulus, notch impact strength, haze and light transmission under the same measurement conditions. Table 4 below summarizes the results of the comparative examples.

4. Discussion of Results The samples of Examples 1 to 7 showed significantly improved haze, light transmittance, or tensile modulus over the non-impact modified polyamide (A) of Comparative Example 17 without significantly impairing haze, light transmittance, or tensile modulus. Indicates notched impact strength.
Other impact modifiers in polyamide (A) impair haze, light transmission or tensile modulus, as can be seen from Comparative Examples 8-11.
The impact modifier (B) causes a significant deterioration of haze, light transmittance or tensile modulus in other amorphous polyamides, as shown in Comparative Examples 12-16.

Claims (16)

Polyamide molding material containing or consisting of the following components (A) to (D):
(A) 55 to 94 % by weight of at least one amorphous copolyamide formed from monomers (a1) to (a4):
(a1) 25 to 40 mol% of at least one acyclic aliphatic diamine having 6 to 10 carbon atoms;
(a2) 10 to 25 mol% of at least one alicyclic diamine having 6 to 36 carbon atoms;
(a3) 20 to 40 mol% of at least one aromatic dicarboxylic acid;
(a4) 10 to 30 mol% of at least one acyclic aliphatic dicarboxylic acid having 8 to 16 carbon atoms;
Here, the ratio of monomers (a1) and (a2) is related to the total of diamines used, which is 50 mol% in total, and the ratio of monomers (a3) and (a4) is the total of dicarboxylic acids used. The total amount is 50 mol%;
(B) 3 to 22% by weight of at least one functional styrene-butadiene -styrene-triblock copolymer, wherein said functionalized styrene-butadiene-styrene-triblock copolymer is styrene-butadiene-styrene-triblock copolymer; the block copolymer is functionalized by copolymerization and/or by grafting with a compound selected from the group consisting of unsaturated carboxylic acids, unsaturated carboxylic acid derivatives, and unsaturated glycidyl compounds;
(C) 3 to 15% by weight of at least one aliphatic partially crystalline polyamide selected from the group consisting of PA6/12 and PA612; and (D) 0 to 8% by weight of at least one addition. Agent Here, the proportions of the components (A) to (D) are 100% by weight in total. The proportion of component (A) in the polyamide molding material is in the range of 61 to 94 % by weight, based on the total weight of the polyamide molding material, and/or the proportion of component (B) in the polyamide molding material is 3 to 20 % by weight based on the total weight of the polyamide molding material, and/or the proportion of component (C) in the polyamide molding material is 3 to 13% by weight based on the total weight of the polyamide molding material. % and/or the proportion of component (D) in the polyamide molding material is in the range from 0 to 6% by weight, based on the total weight of the polyamide molding material. The polyamide molding material described in . ・The haze of the polyamide molding material measured in accordance with ASTM D1003 of a molded article (width and length: 60 x 60 mm, 2 mm thick plate) manufactured from the polyamide molding material is at most 20 % , and/or - a molded article (width and length: 60 x 60 mm, 2 mm thick plate) manufactured from the polyamide molding material has a transmittance of at least 80 % when measured according to ASTM D1003, and/or - the polyamide molding material the molded article produced from said polyamide molding material has a tensile modulus measured according to ISO 527 of at least 1500 MPa, and/or the molded article produced from said polyamide molding composition has a tensile modulus of elasticity measured according to ISO 527 of at least 18 kJ/ m ² Polyamide molding material according to claim 1 or 2, characterized in that it has a notch impact strength measured by 179/2 eA. Monomer (a1) is a linear or branched diamine having 6 to 8 carbon atoms , and /or Monomer (a2) is a cycloaliphatic diamine having 12 to 20 carbon atoms , and /or or Monomer (a3) is an aromatic dicarboxylic acid having 6 to 36 carbon atoms, and /or Monomer (a4) is an acyclic linear or branched dicarboxylic acid having 10 to 14 carbon atoms. is an aliphatic dicarboxylic acid
The polyamide molding material according to any one of claims 1 to 3, characterized in that: Polyamide molding material according to any one of claims 1 to 4, characterized in that monomer (a3) is a mixture of terephthalic acid and isophthalic acid. - The proportion of monomer (a1) in the copolyamide is in the range of 27.5 to 40 mol%, and/or - The proportion of monomer (a2) in the copolyamide is in the range of 10 to 22.5 mol%. range ,
In this case, the proportion of monomers (a1) and (a2) is related to the total of diamines used, and the total is 50 mol%;
and/or the proportion of monomer (a3) in the copolyamide is in the range of 25 to 40 mol%, and/or the proportion of monomer (a4) in the copolyamide is in the range of 10 to 25 mol% surrounded by
In this case, the proportion of monomers (a3) and (a4) is related to the total dicarboxylic acid used, and is 50 mol% in total, according to any one of claims 1 to 5. Polyamide molding material as described. - Monomer (a1) is 1,6-hexamethylene diamine;
- monomer (a2) is selected from the group consisting of bis(4-amino-3-methylcyclohexyl)methane (MACM), bis(4-amino-cyclohexyl)methane (PACM) and mixtures thereof ;
- monomer (a3) is selected from the group consisting of terephthalic acid, isophthalic acid, and mixtures thereof;
- Monomer (a4) is dodecanedioic acid;
Here, the ratio of monomers (a1) and (a2) is related to the total of diamines used, which is 50 mol% in total, and the ratio of monomers (a3) and (a4) is the total of dicarboxylic acids used. Polyamide molding material according to any one of claims 1 to 6, characterized in that it contains a total of 50 mol%. Component (B) is a linear triblock copolymer consisting of one butadiene block and two styrene blocks, and in this case, the proportion of styrene in the styrene-butadiene-styrene-triblock copolymer is 25 to 53. weight %
The polyamide molding material according to any one of claims 1 to 7, characterized in that: Any one of claims 1 to 8, wherein the unsaturated carboxylic acid derivative is a compound selected from the group consisting of unsaturated carboxylic esters and unsaturated carboxylic anhydrides. The polyamide molding material described in . When component (B) is produced by copolymerization, the weight proportions of the individual compounds used for the copolymerization are each in the range from 3 to 20 % by weight relative to the total weight of component (B), and/ or when component (B) is produced by grafting, the weight proportion of the individual compounds used for grafting is 0.4 to 2.0% by weight, respectively, based on the total weight of component (B). Polyamide molding material according to any one of claims 1 to 9 , characterized in that the polyamide molding material is in the range. Polyamide molding material according to any one of claims 1 to 10, characterized in that component (C) is a copolyamide PA6/12 formed from ε-caprolactam and 12-laurinlactam. The additive (D) includes inorganic and organic stabilizers ( antioxidants, antiozonants, and photoprotectants, and the photoprotectants include UV stabilizers, UV absorbers , and UV blockers). lubricants , colorants, marking agents, pigments, carbon black, graphite, graphene, carbon nanotubes, photochromic agents, antistatic agents, mold release agents, condensation catalysts, chain regulators, antifoaming agents, antiblocking agents, Chain extension additives, optical brighteners, IR absorbers, NIR absorbers, halogen-containing flame retardants, non-halogen flame retardants, natural layered silicates, synthetic layered silicates, metallic pigments, metal flakes, metal-coated particles, be selected from the group consisting of granular fillers, fibrous fillers, nanoscale fillers (having a particle size ( _d95 ) of 100 nm or less as measured by laser diffraction according to ISO 13320 (2009)) and mixtures thereof; Polyamide molding material according to any one of claims 1 to 11, characterized by: The fibrous filler is selected from the group consisting of glass fibers, carbon fibers, metal fibers, aramid fibers, vegetable fibers, cellulose fibers ( including nanocellulose fibers) , polymer fibers, whiskers, mineral fibers, and mixtures thereof. Polyamide molding material according to claim 12, characterized in that: A molded article that can be produced from the polyamide molding material according to any one of claims 1 to 13. The molded product may include decorative articles ( including decorative articles for automobile interiors and fashion fields) , sports articles ( including ski boots and soles of sports shoes), leisure articles, and toys (structural elements, components, and shapes). household items (including containers , plates, bowls, cans, beakers, baby bottles, drinking bottles ) , components of kitchen utensils, components of eyeglasses (including eyeglass frames and eyeglass side pieces) (including components for safety goggles, sports goggles and ski goggles), furniture covers, insoles, components and equipment for instruments in the hygiene and cosmetics sectors, parts for safety shoes , caps , filter cups , examination glasses, flowmeters, rupture discs, containers, housings or housing parts for electrical and electronic equipment ( shaving instruments, hair removal instruments, measuring instruments, infrared keys, mobile phones, players, personal digital assistants (PDAs), smartphones , and housings or housing parts for storage media ( including USB sticks ) , protective covers for mobile phones, trim parts in the computer and telecommunications sector, pipes, hoses, films, and parts for electronic cigarettes. Molded article according to claim 14, characterized in that it is selected. Decorative products ( including decorative products in the interior of automobiles and in the fashion sector) , sporting goods ( including the soles of ski boots and sports shoes) , leisure goods, toys ( including structural elements, components, figures and models), household goods ( including containers, dishes, bowls, cans, beakers, baby bottles, drinking bottles) , components of kitchen utensils, components of eyeglasses ( including eyeglass frames and eyeglass side pieces; safety goggles, sports goggles and ski goggles) (including components for goggles), furniture covers, insoles, components and equipment for instruments in the sanitary and cosmetic fields, parts for safety shoes , caps , filter cups, examination glasses, flowmeters, rupture discs. , containers, housings or housing parts for electrical and electronic equipment ( shaving instruments, hair removal instruments, measuring instruments, infrared keys, mobile phones, players, personal digital assistants (PDAs), smartphones , and storage media ( including USB sticks) ( including housings or housing parts for electronic cigarettes) , protective covers for mobile phones, trim parts in the computer and telecommunications sector, pipes, hoses, films, and parts for electronic cigarettes. , use of a polyamide molding material according to any one of claims 1 to 13.